JPH0632990A - Production of metallizable azo compound - Google Patents

Abstract

PURPOSE:To produce the subject compd. in a high yield without producing a by-product and without using a special apparatus by subjecting a diazo component and beta-naphthol to coupling in the presence of an org. amine. CONSTITUTION:The compd. of formula II is produced by subjecting a diazo component of formula I and beta-naphthol to coupling in the presence of an org. amine. The diazo component is prepd. by diazotizing 1-amino-2-naphthol-4- sulfonic acid or 1-amino-6-nitro-2-naphthol-4-sulfonic acid. An alkanolamine is esp. pref. as the org. amine.

Description

Detailed Description of the Invention

FIELD OF THE INVENTION The present invention relates to an improved method for producing a metallizable azo compound.

[0002]

2. Description of the Related Art Conventionally, general formula (2)

[0003]

[Chemical-3]

The azo compound represented by is produced, for example, by the following method.

That is, 1-diazo-2-naphthol-
4-sulfonic acid or 1-diazo-6-nitro-2-naphthol-4-sulfonic acid is made into a weakly acidic aqueous solution using an alkali metal hydroxide, and β-naphthol is an alkaline aqueous solution obtained by using an alkali metal hydroxide. Liquid, then 30 ~
This is a method of performing a coupling reaction at 70 ° C.

However, since the above coupling reaction is slow and many side products are generated by side reactions, various improved methods have been studied. For example, a method of performing a coupling reaction in the presence of a zinc salt, or in the presence of a calcium salt or a magnesium salt, ammonium chloride / ammonia, sodium dihydrogen phosphate for the purpose of improving the yield and suppressing byproducts. / Coupling in a buffer mixture such as sodium hydroxide has been proposed (JP-A-1-101376, JP-A-2-2697).
No. 73, etc.). Further, Japanese Patent Laid-Open No. 61-254550 proposes coupling in a nitrogen atmosphere.

[0007]

However, each of these conventional techniques has the following problems. Coupling in the presence of zinc salt, calcium salt and magnesium salt improves the yield to some extent, but it has the drawback that a troublesome salt is included after the completion of the reaction. In order to synthesize the dye, it is necessary to add a step such as filtration to desalt. Further, the metal complex salt dye thus obtained has a problem that it contains a large amount of water-insoluble by-products formed during the coupling reaction.

The coupling reaction in a buffer mixture of ammonium chloride / ammonia, sodium dihydrogen phosphate / sodium hydroxide, etc. also improves the yield to some extent, but contains a large amount of inorganic salt after completion of the reaction. Therefore, it is not possible to increase the concentration of the metal complex salt dye after metallization, and for that purpose, it is also necessary to include a filtration step after the coupling reaction to separate the inorganic salt. Further, when a metal complex salt dye metallized after coupling in a buffer mixture is used for dyeing a polyamide fiber, there is a problem that a water-insoluble by-product generated during coupling causes staining and other dyeing operations. Furthermore, performing the reaction in nitrogen requires a special device and is not sufficient in improving the yield.

The object of the present invention is to suppress the by-products and to produce the desired azo compound in a high yield without using a special device, and to add a step such as filtration to the azo compound. It is an object of the present invention to provide a method for producing a metallizable azo compound which can be metallized without any treatment to obtain a high-concentration metal complex dye solution.

[0010]

The present invention provides the following general formula (1):

[0011]

[Chemical-4]

A diazo component represented by the formula (wherein X is a hydrogen atom or a nitro group) and β-naphthol are coupled to each other to form a compound represented by the general formula (2).

[0013]

[Chemical-5]

In the method for producing an azo compound represented by the formula, X represents the above-mentioned meaning and M represents an organic ammonium cation or an alkali metal ion.
A method for producing a metallizable azo compound, which comprises performing a coupling reaction in the presence of organic amines.

The method of the present invention will be described in detail below. Specific examples of the diazo component represented by the general formula (1) in the present invention include 1-amino-2-naphthol-4-sulfonic acid or 1-amino-6-nitro-2-naphthol-4-sulfonic acid. Can be obtained by diazotization by a conventional method. For example, the diazo component is weakly acidic, preferably pH.
It is used as an aqueous solution of 2 to 4. At this time, organic amines and / or caustic soda can be used for neutralization.

On the other hand, β-naphthol is used by dissolving it in water using organic amines and / or caustic soda, usually under heating. The amount of β-naphthol used in this case is usually 1 to 1.2 mol, preferably 1.05 to 1.1 mol, relative to 1 mol of the diazo component represented by the general formula (1).

Specific examples of the organic amines used in the method of the present invention include ethylamine, propylamine, butylamine, dimethylamine, diethylamine,
Dibutylamine, triethylamine, tributylamine, cyclohexylamine, ethylenediamine, 1,2
-Alkylamines such as diaminopropane and 1,3-diaminopropane, 3-aminopropanol, isopropanolamine, N-methylethanolamine, diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, N-methyldiethanolamine, N -Ethyldiethanolamine, N
-Butyldiethanolamine, diglycolamine, 2
Alkanolamines such as- (isopropylamino) ethanol, 3-methoxypropylamine, 3-ethoxypropylamine, N- (2-methoxyethyl) ethanolamine, alkoxyalkylamines such as 3-isopropoxypropylamine, morpholine, N-methylmorpholine, N-butylmorpholine, N-benzylmorpholine, N- (2-dimethylaminoethyl) morpholine, piperidine, N-ethylpiperidine, N-amylpiperidine, N-benzylpiperidine, piperazine, N-methylpiperazine, N, N'-dimethylpiperazine, N-ethylpiperazine, N, N'-dipropylpiperazine, N,
Examples thereof include cyclic amine compounds such as N'-diethanolpiperazine.

Alkanolamines are particularly preferably used as the organic amines used in the method of the present invention,
Of these, triethanolamine is preferably used.

In the present invention, the addition timing of the organic amines is not particularly limited as long as the organic amines coexist during the coupling reaction. For example, adding to the coupling component before the coupling reaction,
It may be added to the preparation of β-naphthol, which is the coupling component, or during the preparation of the diazo component represented by the general formula (1), or it may be added simultaneously with the coupling reaction.

The amount of the organic amines added is usually 0.5 with respect to 1 mol of the diazo component represented by the general formula (1).
˜3.0 mol, preferably 1.0 to 2.0 mol.

In the present invention, the coupling reaction is carried out according to a known method. For example, an aqueous solution of a diazo component is usually prepared at 10 to 40 ° C., preferably 25 to 35 ° C. and added to an aqueous solution of β-naphthol. Alternatively, an alkaline aqueous solution of β-naphthol is added to the aqueous solution of the diazo component.

The temperature of the coupling reaction is usually 30 to 7
It is carried out by stirring at 0 ° C and pH 8-11. The reaction time varies depending on the reaction conditions and is not limited, but is usually several minutes to several hours.

After the coupling reaction, the desired azo compound represented by the general formula (2) can be obtained by drying. Further, after the coupling reaction, the azo compound represented by the general formula (2) can be metallized as it is by a known method to obtain a metal complex salt dye.

[0024]

According to the method of the present invention, the coupling reaction proceeds smoothly and the desired azo compound represented by the general formula (2) can be obtained in a high yield and can be obtained by metallizing it. Since a water-insoluble by-product, which is a problem when dyeing a metal complex salt dye, is not generated at all, it has an excellent effect that problems such as contamination do not occur. Further, according to the method of the present invention, a high-concentration dye can be easily obtained industrially by metallization without a step such as filtration after the coupling reaction.

[0025]

EXAMPLES The present invention will be further described below with reference to examples. In the examples, the parts are parts by weight.

Example 1 250 parts of 1-diazo-2-naphthol-4-sulfonic acid was dispersed in 400 parts of water, the temperature was raised to 30 ° C., and 85 parts of 47% caustic soda was added to adjust the pH to 3.0. Dissolved.

Separately, 158 parts of β-naphthol was dispersed in 400 parts of water, heated to 85 ° C., and then triethanolamine 2 was added.
98 parts were added and dissolved. A solution of 1-diazo-2-naphthol-4-sulfonic acid was added thereto over a period of about 1 minute, and the mixture was coupled at 60 ° C. for 2 hours. The coupling yield is 95% of theory.

After completion of the coupling reaction, 650 parts of chromium salicylate solution (chromium content 4%) was added as it was without taking out the azo compound, the temperature was raised to 95 ° C., and the reaction was carried out at the same temperature for 2 hours to complete the chromization. .

The obtained aqueous solution of metal complex salt dye is a stable and high-concentration product as it is, and without drying, it can be used for wool, leather,
Nylon is dyed in a deep dark blue color. There was no contamination of the acetate by water insoluble by-products and filtration of this aqueous dye solution left no residue.

Comparative Example 1 In Example 1, the coupling reaction was carried out in exactly the same manner as in Example 1 except that 132 parts of ammonium sulfate was used instead of triethanolamine. The coupling yield is 90% of theory. However, most of the obtained metal complex salt dyes are precipitated even if they are chromated without taking them out as they are, and in order to prevent this, a step of taking out the azo compound after coupling is necessary. The obtained complex salt dye aqueous solution is not stable as it is,
It must be dried before use. Moreover, this metal complex dye contains a by-product which is insoluble in water, and contaminates the acetate in yellow, and when the dye aqueous solution is filtered, many residues remain.

Example 2 295 parts of 1-diazo-6-nitro-2-naphthol-4-sulfonic acid was dispersed in 400 parts of water and 127 parts of 47% caustic soda was added to adjust the pH to 3.0. Dissolved.

Separately, 158 parts of β-naphthol was dispersed in 400 parts of water, heated to 50 ° C., and then triethanolamine 2 was added.
98 parts were added and dissolved. To this, a solution of 1-diazo-6-nitro-2-naphthol-4-sulfonic acid was added over a period of about 1 minute, and coupling was performed at 35 ° C for 2 hours. The coupling yield is 95% of theory.

After completion of the coupling reaction, 650 parts of chromium salicylate solution (chromium content 4%) was added as it was without taking out the azo compound, the temperature was raised to 95 ° C., and the reaction was carried out at the same temperature for 2 hours to complete the chromization. .

The obtained aqueous dye solution was a stable and highly concentrated product as it was, and dyed wool, leather and nylon in a clear black color without drying. There was no contamination of the acetate by water insoluble by-products and filtration of this aqueous dye solution left no residue.

Example 3 250 parts of 1-diazo-2-naphthol-4-sulfonic acid was dispersed in 400 parts of water, the temperature was raised to 30 ° C., and 85 parts of 47% caustic soda was added to adjust the pH to 3.0. Dissolved.

Separately, 158 parts of β-naphthol was dispersed in 400 parts of water, and the temperature was raised to 85 ° C., followed by diethanolamine 21.
0 part was added and dissolved. To this, 1-diazo-2-naphthol-4-sulfonic acid solution was added in about 1 minute,
Coupling was carried out at 60 ° C. for 2 hours. The coupling yield is 93% of theory.

After completion of the coupling reaction, 650 parts of chromium salicylate solution (chromium content 4%) was added as it was without taking out the azo compound, the temperature was raised to 95 ° C., and the reaction was carried out at the same temperature for 2 hours to complete the chromization. .

The obtained aqueous dye solution was a stable and highly concentrated product as it was, and wool, leather and nylon were dyed in a clear dark blue color without drying. There was no contamination of the acetate by water insoluble by-products and filtration of this aqueous dye solution left no residue.

Example 4 295 parts of 1-diazo-6-nitro-2-naphthol-4-sulfonic acid were dispersed in 400 parts of water and 127 parts of 47% caustic soda was added to adjust the pH to 3.0. Dissolved.

Separately, 158 parts of β-naphthol was dispersed in 400 parts of water, and the temperature was raised to 50 ° C., followed by diethanolamine 21.
0 part was added and dissolved. To this, a solution of 1-diazo-6-nitro-2-naphthol-4-sulfonic acid was added over a period of about 1 minute, and coupling was performed at 35 ° C for 2 hours. The coupling yield is 94% of theory.

After completion of the coupling reaction, 650 parts of chromium salicylate solution (chromium content 4%) was added as it was without taking out the azo compound, the temperature was raised to 95 ° C., and the reaction was carried out at the same temperature for 2 hours to complete the chromization. .

The obtained aqueous dye solution was a stable and highly concentrated product as it was, and dyed wool, leather and nylon in a clear black color without drying. There was no contamination of the acetate by water insoluble by-products and filtration of this aqueous dye solution left no residue.

Example 5 250 parts of 1-diazo-2-naphthol-4-sulfonic acid was dispersed in 400 parts of water, the temperature was raised to 30 ° C., and 85 parts of 47% caustic soda was added to adjust the pH to 3.0. Dissolved.

Separately, 158 parts of β-naphthol was dispersed in 400 parts of water, and the temperature was raised to 85 ° C., and then monoethanolamine 1 was added.
22 parts was added and dissolved. A solution of 1-diazo-2-naphthol-4-sulfonic acid was added thereto over a period of about 1 minute, and the mixture was coupled at 60 ° C. for 2 hours. The coupling yield is 92% of theory.

After completion of the coupling reaction, 650 parts of chromium salicylate solution (chromium content 4%) was added as it was without taking out the azo compound, the temperature was raised to 95 ° C., and the reaction was carried out at the same temperature for 2 hours to complete the chromization. .

The resulting aqueous dye solution was a stable, highly concentrated product, and wool, leather, and nylon were dyed in a clear dark blue color without drying. There was no contamination of the acetate by water insoluble by-products and filtration of this aqueous dye solution left no residue.

Example 6 295 parts of 1-diazo-6-nitro-2-naphthol-4-sulfonic acid were dispersed in 400 parts of water and 127 parts of 47% caustic soda was added to adjust the pH to 3.0. Dissolved.

Separately, 158 parts of β-naphthol was dispersed in 400 parts of water, heated to 50 ° C., and monoethanolamine 1 was added.
22 parts was added and dissolved. To this, a solution of 1-diazo-6-nitro-2-naphthol-4-sulfonic acid was added over a period of about 1 minute, and coupling was performed at 35 ° C for 2 hours. The coupling yield is 93% of theory.

After completion of the coupling reaction, 650 parts of chromium salicylate solution (chromium content 4%) was added as it was without taking out the azo compound, the temperature was raised to 95 ° C., and the reaction was carried out at the same temperature for 2 hours to complete the chromization. .

The resulting aqueous dye solution was a stable and highly concentrated product as it was, and dyed wool, leather and nylon in a clear black color without drying. There was no contamination of the acetate by water insoluble by-products and filtration of this aqueous dye solution left no residue.

Example 7 250 parts of 1-diazo-2-naphthol-4-sulfonic acid was dispersed in 400 parts of water, the temperature was raised to 30 ° C., and 85 parts of 47% caustic soda was added to adjust the pH to 3.0. Dissolved.

Separately, 158 parts of β-naphthol was dispersed in 400 parts of water, and the temperature was raised to 85 ° C.
Parts were added and dissolved. To this, 1-diazo-2-naphthol-4-sulfonic acid solution was added for about 1 minute, and 6
Coupling was carried out at 0 ° C. for 2 hours. The coupling yield is 85% of theory.

After completion of the coupling reaction, 650 parts of chromium salicylate solution (chromium content 4%) was added as it was without taking out the azo compound, the temperature was raised to 95 ° C., and the reaction was carried out at the same temperature for 2 hours to complete the chromization. .

The resulting aqueous dye solution was a stable and highly concentrated product, and wool, leather and nylon were dyed in a clear dark blue color without drying. There was no contamination of the acetate by water insoluble by-products and filtration of this aqueous dye solution left no residue.

Example 8 295 parts of 1-diazo-6-nitro-2-naphthol-4-sulfonic acid were dispersed in 400 parts of water and 127 parts of 47% caustic soda was added to adjust the pH to 3.0. Dissolved.

Separately, 158 parts of β-naphthol was dispersed in 400 parts of water and the temperature was raised to 50 ° C., then triethylamine 202 was added.
Parts were added and dissolved. To this, a solution of 1-diazo-6-nitro-2-naphthol-4-sulfonic acid was added over a period of about 1 minute, and coupling was performed at 35 ° C for 2 hours. The coupling yield is 93% of theory.

After completion of the coupling reaction, 650 parts of chromium salicylate solution (chromium content 4%) was added as it was without taking out the azo compound, the temperature was raised to 95 ° C., and the reaction was carried out at the same temperature for 2 hours to complete the chromization. .

The resulting aqueous dye solution was a stable and highly concentrated product, and dyed wool, leather and nylon in a clear black color without drying. There was no contamination of the acetate by water insoluble by-products and filtration of this aqueous dye solution left no residue.

Claims (3)

[Claims] 1. The following general formula (1): A diazo component represented by the formula (wherein X is a hydrogen atom or a nitro group) and β-naphthol are coupled to each other to form a compound represented by the general formula (2): (In the formula, X represents the above meaning, and M is an organic ammonium cation or an alkali metal ion.) In the method for producing a metallizable azo compound, a coupling reaction in the presence of an organic amine is performed. A method for producing a metallizable azo compound, comprising: 2. The method for producing a metallizable azo compound according to claim 1, wherein the organic amine is an alkanolamine. 3. The metallization according to claim 1 or 2, wherein the organic amine is used in an amount of 0.5 to 3 mol times with respect to the diazo component represented by the general formula (1). Method for producing possible azo compounds. [0001]